Water-soluble dyestuffs containing halogenated cyclobutene or cyclobutane carboxamide groups



Unitcd States Patent O ABSTRACT OF THE DISCLOSURE Water-soluble fiber-reactive dyestufis containing, as reactive groupings, at least one of the moieties C12COF2 ClC-CFz -lTICOC- I R: and I]ICOO(|JR:

R 1 R1 R R1 in which R is hydrogen, chlorine or lower alkyl, R is hydrogen or lower alkyl and R is hydrogen or methyl,

said dyestuffs being suitable for the dyeing or printing of cel'lulosic or protein-containing fibrous materials.

The present invention provides water-soluble dyestuffs and a process for preparing them; more particularly, it provides water-soluble dyestuffs of one of the general Formulae 1 and 2 X F (Kata. A 3 -Rg L l h R1 11 (l) in which A represents the radical of any organic dyestufi molecule, R and R each represent a hydrogen or a chlorine atom or a oarboxylic acid, cyano, nitro or sulfonic acid group or a group R', OR', -COOR, -SO NRN'R, SO R or CO -NR'- and the two substituents R may represent together a further carbon linkage between carbon atoms C and C R and R" each stand for a hydrogen atom or an alkyl or aryl group, R for an alkyl or aryl group, X represents a hydrogen or halogen atom, advantageously a fluorine or chlorine atom, and n is an integer from 1 to 5.

We have found that valuable Water-soluble dyestuffs of the above Formulae l and 2, respectively, can be obtained by reacting 1 mol of a dyestuif of the general formula A-Z in which A is defined as above, m is an integer from 1 to 5 and Z represents (a) an amino group or (b) a reactive halogen atom at the aromatic system of the dyestutf molecule, which halogen atom is linked directly or via a carbonyl or sulfonyl group to the aromatic system, with 1 to 5 mols of a compound of one of the general Formulae 3 and 4 ICC in which R R and X have the meanings given above and B represents one of the groupings --CO'-halogen, sO -halogen, CH CH SO -halogen, CH=CHOO-halogen and OHRCHR--CO- halogen, if Z is an amino group, or an alky1ene-NH group, if Z is a halogen atom, at a temperature between about 0 C. and about C., advantageously between about 10 C. and about 30 C., in an aqueous, aqueousorganic or exclusively organic medium at a pH-value between about 6.5 and about 10* in the presence of an acid-binding agent.

As dyestuffs A there may be used, for example, manoazo, disazo and trisazo dyestuffs, dyestutfs of the triphenylmethane, anthraquinone, phthalocyanine, nitro, acridone, oxazine, dioxazine, indigoid or thioindigoid series, derivatives of perylenetetnacarboxylic acid and thiazole and acridine dyestuffs.

As reaction components of the above Formulae 3 and 4 respectively, the following compounds may be used, for example 2,2 dichloro 3,3 difluorocyclobutanecarboxylic acid chloride-1, 3-(2,2'-dichloro-3-difluorocyclobutyl)-acrylic acid chloride, 3-(2',2'-dichloro-3,3'- difluono-4'-methylcyclobutyl)acrylic acid chloride, 2- ch-loro 3,3 difiuorocyclobutene 1 oarboxylic acid chloride-1, 1,2,2 trichloro 2,2 difiuorocyclobutanecarboxylic acid chloride-1.

The compounds of Formulae 3 and 4, respectively, to

be reacted in accordance with the invention may be obtained by reaction of unsaturated nitriles under pressure at elevated temperatures with halogenated olefins, subsequent saponification to halogenated cyclobutanecarboxylic acids and further reaction yielding carboxylic acid halides. The said cylcobutanecarboxylic acid halides may also be obtained by reacting unsaturated carboxylic acids with halogenated olefins under the above conditions, converting the halogenated cyclobutanecarboxylic acids so obtained to the corresponding acid halide by known processes, or by direct synthesis of the lhalides of unsaturated carboxylic acids with halogenated olefins (cf. US. Patents Nos. 2,441,128 and 2,462,345). The above mentioned compounds to be reacted in accordance with the invention can also be obtained by converting the abovementioned nitriles into amines in known manner.

When the reaction is carried out in an aqueous or aqueous-organic medium, it is advantageous to use hydroxides, carbonates or hydrogen carbonates of the metals of the first to third group of the Periodic System as acid binding agents, advantageously the sodium compounds. When the reaction is carried out in an organic medium, tertiary organic bases such as, for example, dimethylaniline, pyridine or picoline are preferably used as acid binding agents.

The reaction according to the present invention may also be carried out at a temperature above or below the temperature range indicated above; however, if the reaction is carried out at lower temperatures, the reaction times are correspondingly longer and if the reaction is carried out at higher temperatures, the yields are smaller. The optimum temperature to be used in each individual case depends on the reaction components used.

The dystuffs obtainable by the process of the invention give dyeings and prints of very good fastness properties on fibrous materials of native or regenerated cellulose such as, for example, cotton, linen, hemp, staple fibers or rayon, or of native or regenerated protein fibers such as, for example, wool or silk.

Dyeings are advantageously obtained by impregnating the fibrous material with the dyestulfs in the pres ence of agents having an alkaline reaction or by dyeing it in a long liquor. If the dyestufI has no or no pronounced atfinity for the fibrous material, it is advantageous to impregnate the fibrous material in the cold or at moderate temperature with an aqueous solution of the dyestuff, which solution may contain a salt, and then to squeeze 01?. The dyestuff solutions may contain inorganic salts such as, for example, alkali metal chlorides or alkali metal sulfates. As agents having an alkaline reaction there are advantageously used inorganic compounds such as, for example, alkali or alkaline earth metal hydroxides, alkali metal bicarbonates, alkali metal carbonates, alkali metal phosphates such as trisodium phosphate or mixtures of disodium phosphate and trisodium phosphate, alkali metal borates or alkali metal salts of trichloracetic acid, or mixtures of such agents having an alkaline reaction.

The dyestuffs so applied to the fibrous material are thermo-set after impregnation. The impregnated material is subjected to a heat treatment, if desired after intermediate drying. The heat treatment is carried out by steaming, in a heated current of air or in an organic sol- 'vent. If, for example, alkali metal hydroxides are used, setting may already be carried out in the cold or at moderately elevated temperature by abandoning the impregnated material for several hours.

When impregnating baths free from agents having an alkaline reaction are used, the impregnated material is advantageously introduced into a salt-containing alkali bath and subsequently subjected to a heat treatment. By using an appropriate combination of temperature and pH-value and choosing an appropriate alkali, the dyestuifs may also be thermo-set during dyeing.

It is also possible to apply the dyestuifs of the invention to the fibrous material by textile printing. To make the printing colours, the dyestuffs are dissolved in water, if desired with addition of conventional auxiliary agents, for example, hygroscopic substances or solution promoters such as urea, acetamide or dimethyl sulfoxide, and while adding dispersants, and stirred with thickening agents such as methyl cellulose, starch ether, alginate thickeners or emulsion thickeners (oil-in-water or water-in-oil types with or without addition of further thickeners) The pastes so obtained are then mixed with the above alkalies and the material is printed in usual manner. Thermo-setting is then brought about by a heat treatment with steam carried out, for example, for 5 to minutes at 101 to 105 C. or for about 30 seconds to 1 minute at 145 to 150 C., or by treating with dry heat for several minutes at, for example, 120 to 150 C. or for about 30 seconds to 1 minute at 190 to 220 C.

The above mentioned temperatures and thermosetting times may be modified depending on the nature and quantity of the alkali used.

The fibrous material may also be printed with substantially neutral or even weakly acid printing pastes flee from agent having an alkaline reaction. In this case, the fibrous material must be treated, before or after printing, with an agent having an alkaline reaction. The dyestufi is thermo-set by treating with steam or applying heat,,the period of time for which it is treated and the temperature depending on the nature and quantity of the alkali.

It is also possible to thermo-set the dyestuff by a short passage through a hot salt-containing alkaline solution without steaming.

The following examples serve to illustrate the invention but they are not intended to limit it thereto, the parts being by weight unless otherwise stated and the relationship of parts by volume being the same as that of the kilogram to the liter:

Example 1 45.3 parts of the aminoazo compound obtained by coupling diazotized 4-acetylamino-l-arninobenzene-Z-sultonic acid with 1-(4'-sulfopheny1)-3-metl1yl-5-pyrazolone and hydrolytically splitting oif the acetyl group in aqueous solution with sodium hydroxide solution, were adjusted to pH 8 with 2 N-sodium carbonate solution. 22.3 parts of 2,2. dichloro-3,3-difluorocyclobutanecarboxylic acid chloride-1 dissolved in 50 parts by volume of acetone in one instance and 50 parts by volume of dioxane in another instance, and simultaneously a 2 N- sodium carbonate solution were then added dropwise in a manner such that the solution was maintained at a pH of 7.5 to 8. The whole was then acidified with acetic acid, a saturated sodium chloride solution was added and the dyestufi of the formula HO/N precipitated and was filtered.

When applied to cotton in an alkaline bath, the dyestuif gave reddish yellow dyeings that had very good wet fastness properties.

A cotton fabric was printed using sodium bicarbonate as the alkali and after thermo-setting in a continuously operating steamer and processing according to the customary methods for reactive dyestufis, a reddish yellow print of very good properties of wet fastness was obtained.

Example 2 44.8 parts of the aminoazo compound obtained by cou pling diazotized 1-acetylamino-3-aminobenzene-4-sulfonic acid with 1-(3'-sulfophenyl)5-pyrazolone-3-carboxylic acid and hydrolytically splitting off the acetyl group in aqueous solution with sodium hydroxide solution, were reacted with 18.6 parts of 2-chloro-3,3- difiutorocycllobutene-l-carboxylic acid chloride -1 under the conditions described in Example 1.

The dyestuff of the formula was obtained.

When applied from an alkaline bath, the dyestuff gave a greenish yellow dyeing on cotton that had good properties of wet fastness.

By using the sodium salt of trichloracetic acid as the alkali and thermo-setting for 20 minutes in a Stern steamer, a greenish yellow print of good properties of wet fastness was obtained on cotton.

Example 3 45.3 parts of the aminoazo compound obtained by couplmg diazotized 1-aminobenzene-2,5-disulfonic acid with 1-(3'-aminophenyl) -3-methyl-5-pyrazolone, were acylated with 25.7 parts of 1,2,2-trichloro-3,3-difluorocyclobutanecarboxylic acid chloride -1 under the conditions described in Example 1. The dyestuif of the formula SOKH was obtained which when applied to cotton in an alkaline bath gave reddish yellow dyeings of very good properties of wet fastness. 7

When viscose rayon was printed with a printing paste containing, in addition to the dyestuif, urea and sodium bicarbonate as the alkali and the dyestuif was thermo-set in a continuously operating steamer (type Mather-Flatt), a reddish yellow print that had a good fastness to washing was obtained.

Example 4 22.3 parts of 2,2-dichloro-3,3-difluorocyclobutanecarboxylic acid chloride-1 were reacted under the conditions described in Example 1 with 40.7 parts of the aminoazo compound obtained by coupling diazotized 2- aminonaphthalenel,8-disulfonic acid with aniline in an acid medium.

The dyestuif of the formula I SOQH Example 5 By acylating 42.3 parts of the aminoazo compound obtained by coupling diazotized l-aminobenzene-Z-sulfonic acid with Z-amino-5-hydroxynaphthalene-7-sulfonic acid, with 18.6 parts of 2-chloro-3,3-difiuorocyclobutene-l-carboxylic acid chloride-1 in the manner described in Example 1, the dyestuif of the formula.

SO H

was obtained which when applied to cotton in an alkaline bath gave orange red shades of good properties of wet fastness.

When cotton fabric was printed with a neutral printing paste containing the dyestuff and the printed fabric was passed through an alkaline, salt-containing padding liquor and the dyestuif was thermo-set in a two-phase steamer, an orange-colored print of very good properties of wet fastness was obtained.

Example 6 47.2 parts of the aminoazo compound obtained by coupling diazotized 4-chloro-1-aminobenzene-2-sulfonic acid with 2- (N-methylamino -8-hydroxynaphthalene-6-sulfonic acid, were reacted with 25.7 parts of 1,2,2-trichloro-3,3- difluorocyclobutanecarboxylic acid chloride-1 under the conditions described in Example 1.

The dyestuif of the formula was obtained which when applied to fibrous material of regenerated cellulose in an alkaline bath gave a red dyeing of very good properties of wet fastness.

When the dyestulf was printed on cotton fabric in the presence of sodium carbonate, thermo-set and treated in usual manner, a red print of good fastness to washing wa obtained.

Example 7 42.2 parts of the product obtained by coupling diazotized aniline with 1-amino-8-hydroXynaphthalene-3,6-disulfonic acid, were acylated with 25.7 parts of 1,2,2-trichloro-3,3-difiuorocyclobutanecarboxylic acid chloride-1 under the conditions described in Example 1. The dyestulf of the formula l I l H038 -S 03H was obtained which when applied to staple fibers in an alkaline bath gave a red dyeing of very good properties of wet fastness.

When a cotton fabric was printed with a neutral printing paste containing the dyestulf, and the dyestuff was thermo-set by a short passage of the printed fabric through a hot, alkaline, salt-containing bath, a red print of very good properties of wet fastness was obtained.

Example 8 60 parts of the aminoazo compound obtained by coupling diazotized 4-nitro-1-amino benzene-2-sultonic acid with 1 acetylamino-8-hydroXynaphthalene-3,6-disulfonic acid and reducing the nitro group with sodium sulfide to the amino group, were acylated with 18.6 parts of 2- chloro-3,3-difiuorocyclobutene carboxylic acid chloride-1 under the conditions described in Example 1. The dyestuff of the formula was obtained which when applied to cotton from an alkaline bath gave a bluish red dyeing of very good properties of wet fastness.

7 8 1 By using sodium bicarbonate as the alkali in the printchloride-1 under the conditions described in Example 10. ing paste, printing and thermo-setting in a continuously The dyestufi of the formula operating steamer, a bluish red print of good properties of O NH l fastness was obtained. I p H 1 Example 9 S0311 47.5 parts of the disazo dycstuif obtained by coupling diazotized 4- amino-l,1'-azobenzene-3,4'-disulfonic acid with 3-rnethyl-1-aminobenzene, were reacted with 22.3 g parts of 2,2 dichloro 3,3-difluorocyclobutanecarboxylic NH- TSOKH acid chloride-l under the conditions described in Example 10 O H 1. The dyestufi of the formula NH-C C C SIO3H E C12?'CF2 H 0aSN=NN=N-NHC 0 CH-CH2 was obtained which when applied to cotton in an alkaline was obtained which when applied to cotton in an alkaline bath gave a yellow-brown dyeing of very good properties bath giwe a blue dyelllg of good Propeftles of wet fastness' of wet fastnew By printing the dyestuif in the presence of sodium car- By using sodium bicarbonate as the alkali in the printbonat? fabiic and therm0'ettmg the dyest'ufi. by ing paste, printing a staple fiber fabric and thermo-setting i f m a g i opergtmg adbnght the dyestuff, a yellow-brown print of good properties of pun o goo as Hess owas mg was 0 mm wet fastness was obtained. Example 12 76.3 parts of [Cu-phthalocyanine{-SO H) ]-(3'- sul-fo-4'-aminophenyl) sulfonamide obtained by causing a tertiary organic base to act upon a mixture of [Cupints of 1 amino (a.mmop liens/1'4 ammoy phtha'locyanine}(50 (1) and the sodium salt of 1,4 anthraqu1n0ne-2,3 ,5-tr1sulfon1c acid obtained by condendiaminobenzene 3 svulfonic acid in aqueous suspension sation of 1-amino-4-bromo-anthraquinone-2,S-disulfonic were reacted with 257 parts of 12z trichloro 3,3 difiuo Example 10 acid With 1,4-diaminobenlenei3'Slllfonic a i in an aquerocyclobutanecarboxylic acid chloride-l under the reacous-alkallne medium, Were adlusted P 3 with a 2 tion conditions described in Example 1. The dyestuff of sodium carbonate solution. To this batch 22.3 parts of the formula (l)C12-C F2 [Cu-phtalocyauinMSWH)a 3-SO -NH-NHC o- -t:11,

was obtained which when applied to cotton in an alkaline 40 bath gave a greenish blue dyeing of very good properties of wet fastness.

2,2-dichloro-3,3-difluorocyclobutane-carboxylic acid chloride-1 and 2 N-sodium carbonate solution were added dropwise in a manner such that a pH range of 7.5 to 8 Example 13 was maintained. The pH was then ad usted to 2 with con- 36.4 parts of the compound of the formula centrated hydrochloric acid. and the dyestufi of th obtained by reacting 1,4-diaminobenzene-2-sulfonic acid formula at 180 C. with perylenetetracarboxylic acid anhydride E 111131 in quinoline, were suspended in 500 parts by volume of water. A saturated aqueous solution of 110 parts of so- SOHH dium dithionite (Na S O .2H O) was added and the i i whole was adjusted to pH 7.5 with 2 N-sodium carbonate SIOBH C]2C CF2 solution under a nitrogen atmosphere. Subsequently, 22.3

| g 1 parts of 2,2-dich1oro-3,3-difiuorocyclobutanecarboxylic Hoas NH NH COCH CH acid chloride-1 and simultaneously 2 N-sodium carbonate solution were added dropwise in a manner such that a pH range of 7.5 to 8 was maintained. After acidification to obtain a pH of 2 and passing air through at elevated was precipitated by adding sodium chloride. The dyestulf, When applied to cotton in an alkaline bath, gave a greenish blue dyeing of excellent properties of wet fastness.

. By printing the dyestuff in the presence of urea and tmperature j instance or adding an aqueolis solu' sodium carbonate on cotton fabric, thermo-setting and of an OXldlZlllg agent S11C11 y gen peroxlde and after-treating as usual, a greenish blue print of good propsodium Perborate, fespectlvely, In another instance, the erties of fastness was obtained. dyestuff of the formula so H 00 CO S0 11 Example 11 was precipitated.

43 8 parts of 1 amino 4 (aminophenyl 3r amino) 1 part of this dyestufi was dissolved in a solution of anthraquinone-2,4'-disulfonic acid were reacted with 18.6 Parts o Sodium dithionlte in 1000 Parts byvohlme parts of 2-chloro-3,3-difluorocyclobutenecarboxylic acid of water. 10 parts of a cotton fabric were introduced 'into '10 the red-violet solution and moved therein for 30 minutes We claim: after adding parts of a sodium hydroxide solution of 1. A water-soluble dyestufr of the formula strength. By introducing air at a temperature of 80 01 F 1 01 F to 100 C. in one instance or adding a dilute solution l a 1 l of an oxidizing agent such as sodium perborate and hy- 5 'T or I L C3 F A B c "-Rfl A-BC R drogen peroxide, respectively, in another instance, a reddish blue dyeing of very good properties of wet fastness i u H n was obtained on cotton.

In the preparation of the dyestuff as well as in the dyewhergm A Is a waterisoluble i f q q' cyan1ne-, perylene tetracarboxylic acid amide, benzacning process there could be used, instead of the above 10 alkalies, other al-kalies, for example sodium bicarbonate, ffi ggj gf dyestufi radlcal B Is soda, sodium hydroxide solution or tertiary sodium phosphate, and, instead of sodium dithionite, other reducing agents commonly used in va-t dyeing. CH3

The dyeing temperature could also be varied consider- R is hydrogen, chlorine or lower alkyl, R is hydrogen ably. or lower alkyl, and n is 1 or 2.

Example 14 2. The dyestulf of the formula 19 parts of 4-aminoanthraquinone-4-trifluoromethyl-2,

1-(N)-l'2- (N)-benzacridone were reacted with 9.3 parts 20 of 2-ch'loro-3,3-difluorocyclobutenecarboxylic acid chloride-l under the conditions described in Example 13 and subsequently precipitated. The dyestufr" of the formula 010-0 F2 0 T ii NHo0-iiom F 3. The dyestufi of the formula NHCOC H2 H I 010431,! was obtained which, under the dyeing conditions described NH-C o- COH in Example 13, gave a blue dyeing on cotton that had H3 good properties of wet fastness. 4, h d st-ufl f the f l Example 15 5. The dyestufi? of the formula 43 parts of alpha-aminonaphthothioxanthonesulfonic acid of the formula S 50311 v C12C CFg [CuPc(S0 H)n- S0 NH -NHCOCCH1 H038 B 50 J I Pczphthal'oeyanine) 6. The dyestuif of the formula obtained from o-mercaptobenzoic acid and l-aminonaph- O NH thalene in sulfuric acid of a density of 1.84, were ad- H justed to pH 7.5 with 2 =N-sodium carbonate solution and so H acylated by adding dropwise a solution of 21.5 parts of 2-chloro-3,3-difluoro 4,4 dimethylcyclobutenecarboxylic S O H acid chloride-l dissolved in 50 parts by volume of acetone. I g i 3 By simultaneous addition of a further quantity of 2 N- H sodium carbonate solution, the pH was maintained at 7.5 Oas NE NH 00 CH to 8. By acidification with a small amount of glacial acetic acid to obtain a pH of 4 and addition of sodium chloride, The dyes/tutf 0f the formula the dyestuif of the formula O NH,

u BOSS s03H SOSH CH3 I was precipitated. The dyestutf, when applied to cotton in NH-C 0-0 H2 an alkaline bath, gave a khaki-coloured dyeing of very good properties of wet fastness. (References on following page) Referencs Cited UNITED STATES PATENTS Ludwig et a1 260-143 Dickey t a1 260-196 X N-eier et a1 260-162 X Senn 260-162 X Berrie et a1. 260-162 Rohland et a1 260-162 Bowman et a1 260-162 Dehn et a1 260-205 Scherer et a1 2-60-16 3 Scherer et a1 260-3145 FLOYD D. HIGEL, Primary Examiner. 

1. A WATER-SOLUBLE DYESTUFF OF THE FORMULA 